CN101410441B - Method for applying a coating onto a silicone hydrogel lens - Google Patents
Method for applying a coating onto a silicone hydrogel lens Download PDFInfo
- Publication number
- CN101410441B CN101410441B CN2007800111197A CN200780011119A CN101410441B CN 101410441 B CN101410441 B CN 101410441B CN 2007800111197 A CN2007800111197 A CN 2007800111197A CN 200780011119 A CN200780011119 A CN 200780011119A CN 101410441 B CN101410441 B CN 101410441B
- Authority
- CN
- China
- Prior art keywords
- contact lens
- lens
- coating
- siliceous
- siloxanes aquogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 160
- 239000011248 coating agent Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000017 hydrogel Substances 0.000 title claims abstract description 17
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims description 110
- -1 siloxanes Chemical class 0.000 claims description 104
- 239000000178 monomer Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000002474 experimental method Methods 0.000 claims description 37
- 230000002209 hydrophobic effect Effects 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 229920000831 ionic polymer Polymers 0.000 claims description 27
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 230000000845 anti-microbial effect Effects 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 10
- 239000002861 polymer material Substances 0.000 claims description 10
- 229920000447 polyanionic polymer Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 7
- 230000003115 biocidal effect Effects 0.000 claims description 6
- 239000003139 biocide Substances 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003791 organic solvent mixture Substances 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920002851 polycationic polymer Polymers 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 68
- 238000004043 dyeing Methods 0.000 description 34
- YCUVUDODLRLVIC-UHFFFAOYSA-N Sudan black B Chemical compound C1=CC(=C23)NC(C)(C)NC2=CC=CC3=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 YCUVUDODLRLVIC-UHFFFAOYSA-N 0.000 description 28
- 239000010410 layer Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 15
- 238000009736 wetting Methods 0.000 description 15
- 238000012056 up-stream process Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 210000001508 eye Anatomy 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- 210000004087 cornea Anatomy 0.000 description 6
- 230000004438 eyesight Effects 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000002953 phosphate buffered saline Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000005661 hydrophobic surface Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000012487 rinsing solution Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002801 charged material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005574 norbornylene group Chemical group 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NWBTXZPDTSKZJU-UHFFFAOYSA-N 3-[dimethyl(trimethylsilyloxy)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)C NWBTXZPDTSKZJU-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101150055539 HADH gene Proteins 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- SIQACMDVNRDNKW-UHFFFAOYSA-N N,N-dimethylmethanamine 2-hydroxypropyl 2-methylprop-2-enoate Chemical compound CN(C)C.CC(O)COC(=O)C(C)=C SIQACMDVNRDNKW-UHFFFAOYSA-N 0.000 description 1
- HLJYBXJFKDDIBI-UHFFFAOYSA-N O=[PH2]C(=O)C1=CC=CC=C1 Chemical compound O=[PH2]C(=O)C1=CC=CC=C1 HLJYBXJFKDDIBI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001616 Polymacon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000607 artificial tear Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036770 blood supply Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 210000003128 head Anatomy 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229940030216 hypotears Drugs 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940023490 ophthalmic product Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical class CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010106 rotational casting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NLAIHECABDOZBR-UHFFFAOYSA-M sodium 2,2-bis(2-methylprop-2-enoyloxymethyl)butyl 2-methylprop-2-enoate 2-hydroxyethyl 2-methylprop-2-enoate 2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O.CC(=C)C(=O)OCCO.CCC(COC(=O)C(C)=C)(COC(=O)C(C)=C)COC(=O)C(C)=C NLAIHECABDOZBR-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00038—Production of contact lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00865—Applying coatings; tinting; colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Eyeglasses (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a cost-effective method for making a silicone hydrogel contact lens having an LbL coating thereon that is not covalently attached to the lens and has good hydrophilicity, intactness and durability. The method comprises LbL coating at high temperature.
Description
The present invention relates to a kind of hydrophilic polymer that on the siloxanes aquogel contact lens, applies to improve the method for its wetting ability and oilness.In addition, the present invention provides a kind of siloxanes aquogel contact lens with hydrophilic coating of good integrity and weather resistance.
Background of invention
In recent years, soft siloxanes aquogel contact lens, for example, Focus NIGHT&DAY
TMAnd O2OPTIX
TM(all from CIBA VISION) and PureVision
TM(bausch & lomb) is because their high oxygen permeability and comfortableness become becomes more and more popular.Closely the fit shape of eyeball of " soft " contact lens is so oxygen can not easily surround lens.Soft-contact lens must allow oxygen to arrive cornea from ambient air (that is, oxygen), and this is because cornea can not resemble other tissue from blood supply reception oxygen.If enough oxygen can not arrive cornea, then expanding appears in cornea.Anoxic causes the unfavorable growth of blood tissues in cornea for a long time.Through having high oxygen permeability, the siloxanes aquogel contact lens allows enough oxygen to be penetrated into cornea via lens, and corneal health has minimum disadvantageous effect.
But the siloxanes aquogel material has water repellent surface usually or at least a portion surf zone is hydrophobic (can not be wetted).On the water repellent surface or hydrophobic surface regions that is adsorbed to the siloxanes aquogel contact lens from the lipoid or the protein of eyes environment.The water repellent surface of siloxanes aquogel contact lens or hydrophobic surface regions make it attached on the eyes.Therefore, the siloxanes aquogel contact lens generally needs surface-treated to improve surface hydrophilicity.The high surface hydrophilicity of the LbL coating on contact lens and oilness can be improved wearer's comfortableness and/or eye health.
The hydrophobic known method that improves the higher contact lens material of hydrophobicity is to use plasma treatment, for example commercial lens, for example Focus NIGHT&DAY
TMAnd O2OPTIX
TM(all from CIBA VISION) and PureVision
TM(bausch & lomb).Plasma-coated advantage is its weather resistance, higher wetting ability (or good wettability) and to lipoid and proteinic low tolerance deposition with absorb.But the plasma treatment of siloxanes aquogel contact lens is not that cost is effective, and this is because the ready-formed contact lens must be dry before the plasma treatment, with because the higher fund input relevant with plasma processing.
The another kind of hydrophilic method of improving the higher contact lens material of hydrophobicity is that layer polyion property material deposition technique that suffers layer (LbL) is (referring to for example US patent 6,451,871,6,717,929,6; 793,973,6,884,457,6,896; 926,6,926,965,6,940,580).Though this technology can provide cost effectively to make the wetted method of siloxanes aquogel material ability; But this method needs the step of long time and complicacy to apply the LbL hydrophilic coating, and this is coated with course siloxanes aquogel contact lens and gives wetting ability and oilness.The disclosed method that the LbL coating is coated onto on the siloxanes aquogel contact lens can not make the surface have required wetting ability, oilness, weather resistance and/or full surface coverage (that is integrity).
So, still need effectively hydrophilic coating to be coated to the method on the siloxanes aquogel contact lens.
Summary of the invention
On the one hand; The present invention provides a kind of hydrophilic coating is coated to the method on the siloxanes aquogel contact lens; This method comprises: contact lens is contacted with first coating solution of temperature for about 45-95 ℃; Thereby form and the non-covalent undercoat that is connected of contact lens; Wherein first coating solution comprises the polyion material with first hydrophobic backbone and a plurality of ionogenic side groups, and wherein first coating solution has enough low pH to prevent ionogenic group generation ionization basically, and wherein undercoat contains at least one strata ionic material; (b) said contact lens is contacted with the 3rd coating solution of temperature for about 45-95 ℃; Thereby on undercoat, form finishing coat; Wherein second coating solution contains the uncharged hydrophilic polymer with second hydrophobic backbone, and wherein finishing coat contains the said hydrophilic polymer of one deck at least.
On the other hand; The present invention provides a kind of method of making the siloxanes aquogel contact lens; This method may further comprise the steps: (a) form material casting siloxanes aquogel contact lens from the siloxanes aquogel contact lens, wherein said siloxanes aquogel contact lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer has the siliceous big monomer of ethylenically unsaturated group; Crosslinkable siliceous prepolymer, and their mixture; (b) contact lens is contacted with first coating solution of temperature for about 45-95 ℃; Thereby form and the non-covalent undercoat that is connected of contact lens; Wherein first coating solution comprises the polyion polymer materials with first hydrophobic backbone and a plurality of ionizable or charged side group, and wherein undercoat contains at least one strata ionic material; (c) said contact lens is contacted with second coating solution of temperature for about 45-95 ℃; Thereby on undercoat, form finishing coat; Wherein second coating solution contains the uncharged hydrophilic polymer with second hydrophobic backbone, and wherein finishing coat contains the said hydrophilic polymer of one deck at least.
On the other hand, the present invention provides a kind of siloxanes aquogel contact lens.Contact lens of the present invention comprises sandwich layer siloxanes aquogel material and hydrophilic coating; Its center core layer siloxanes aquogel material is the copolymerization product that the siloxanes aquogel contact lens forms material; Wherein said siloxanes aquogel contact lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer; Siliceous big monomer with ethylenically unsaturated group, crosslinkable siliceous prepolymer, and their mixture; Wherein hydrophilic coating does not have covalently bound to sandwich layer siloxanes aquogel material; And comprise innermost layer and the outermost layer that one deck has the uncharged hydrophilic polymer of second hydrophobic backbone that one deck has the polyion material of first hydrophobic backbone; Wherein the siloxanes aquogel contact lens has the oxygen permeability of 40Barrer at least; With average water contact angle be 80 degree or littler be the wettable surface of characteristic and with can through the finger frictional experiment or to repeat to press heat experiment be the good coat weather resistance of characteristic.
From following description to the preferred embodiment for the present invention, these and other aspect of the present invention will be more clear.Said detailed description only is used for explaining the present invention, rather than is used for limiting scope of the present invention, and said scope is limited accompanying claims and equivalent way thereof.For a person skilled in the art, under spirit that does not depart from novel thought of the present disclosure and scope, obviously can make multiple conversion of the present invention and improvement.
The accompanying drawing summary
Fig. 1 shows the equipment that is used for applying to the siloxanes aquogel contact lens LbL coating according to a preferred embodiment of the invention.
Fig. 2 shows that another preferred embodiment according to the present invention is used for applying to the siloxanes aquogel contact lens equipment of LbL coating.
The detailed description of specific embodiments of the present invention
To be described in detail embodiment of the present invention now.To those skilled in the art, obviously can make multiple improvement and conversion in the present invention, and not depart from scope of the present invention or spirit.For example, as the part of an embodiment and explain or embodiment that the characteristic described can be used for another to produce other embodiment.Therefore, the present invention is intended to contain these improvement and the conversion that falls into accompanying claims and equivalent way thereof.During detailing below, other purposes of the present invention, characteristic and aspect obtain openly, or obvious from following detailed description.Concerning those of ordinary skills, be appreciated that this discussion only is the description to exemplary embodiment, and be not intended to limit wideer aspect of the present invention.
Only if definition is arranged in addition, used here all technology and scientific terminology have the identical meanings like those skilled in the art's common sense.Usually, used here nomenclature and experimentation are known, and are commonly used in this area.Employing ordinary method with regard to these processes, as this area and numerous provide in the reference those.When with odd number term being provided, the inventor has also considered the plural number of this term.Here used nomenclature and following experimentation are known and are usually used in this area those.
Term " contact lens " is represented to be placed on adorner's the eyes here or the structure in the eyes.User's eyesight can be proofreaied and correct, improves or changed to contact lens, but must not be this situation.Contact lens can be processed by the suitable material of known suitable material of any prior art or back exploitation, and can be SCL, hard lens or hybrid lens." siloxanes aquogel contact lens " expression contains the contact lens of siloxanes hydrogel material.
" hydrogel " is meant the polymeric materials that when abundant hydration, can absorb at least 10 weight % water.
" siloxanes aquogel " is meant the hydrogel that obtains through the polymerisable compound copolymerization that contains at least a siliceous vinyl monomer or at least a siliceous big monomer or the siliceous prepolymer of at least a crosslinkable property.
What " wetting ability " used herein described is to compare with lipid more easily and water bonded material or its part.
" monomer " is meant polymerisable low-molecular weight compound.Lower molecular weight typically refers to less than 700 daltonian molecular-weight average.
As used herein, " vinyl monomer " but be meant low-molecular weight compound with ethylenically unsaturated group and photochemical polymerization or thermopolymerization.Lower molecular weight typically refers to less than 700 daltonian molecular-weight average.
Term " ethylenically unsaturated group " here uses with broad sense, the meaning be comprise contain at least one＞any group of C=C＜group.Exemplary ethylenically unsaturated group includes, but not limited to acryl, methacryloyl, allyl group, vinyl, styryl or other contains the group of C=C.
As used herein; Curing or the polymeric " photochemical " that relates to polymerisable compound or material is meant that said curing (for example crosslinked and/or polymerization) carries out through actinic radiation, and said actinic radiation for example is UV radiation, ionizing rays (like gamma-rays or x-ray radiation), microwave radiation etc.Thermofixation or photochemical curing are well known to those skilled in the art.
As used herein, " hydrophilic ethylene base monomer " is meant as homopolymer and usually produces water miscible or can absorb the vinyl monomer of the polymkeric substance of at least 10 weight % water.
As used herein, " hydrophobic vinyl monomers " is meant as homopolymer and usually produces non-water-soluble and can absorb the vinyl monomer less than the polymkeric substance of 10 weight % water.
" big monomer " is meant the medium and high-molecular weight compounds or the polymkeric substance that comprise the functional group that can carry out further polymerization and/or crosslinking reaction.Medium and HMW typically refers to greater than 700 daltonian molecular-weight average.Preferably, big monomer comprises ethylenically unsaturated group and can photochemical polymerization or thermopolymerization.
" prepolymer " is meant starting polymer, and it can be by photochemical curing or thermofixation or chemosetting (for example crosslinked and/or polymerization) to obtain molecular weight far above the crosslinked of said starting polymer and/or polymeric polymkeric substance.
" crosslinkable prepolymer " is meant can be under actinic radiation crosslinked starting polymer, obtains having compared with beginning polymkeric substance high-molecular weight cross-linked polymer significantly more.
" crosslinkable siliceous prepolymer " is meant siliceous and can be under actinic radiation crosslinked starting polymer, obtains having compared with beginning polymkeric substance high-molecular weight cross-linked polymer significantly more.
" polymkeric substance " is meant the material that forms through one or more monomers of polymerized/cross-linked.
" main chain " of polymkeric substance is illustrated in the main chain in the polymer molecule.
" initiator " expression can cause the chemical of free radical reaction, can be light trigger or thermal initiator.
" light trigger " refers to through utilizing the chemical of light-initiated radical crosslinking and/or polyreaction.The light trigger that is fit to comprises; But be not limited to; Benzoin methyl ether, diethoxy acetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenylketone,
type and
type, preferred
1173 and
2959.
" thermal initiator " refers to through utilizing heat energy to cause the chemical of radical crosslinking and/or polyreaction.The instance of the thermal initiator that is fit to includes, but not limited to 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), superoxide such as Lucidol etc.Preferred thermal initiator is Diisopropyl azodicarboxylate (AIBN).
" space constraint of actinic radiation " a kind of effect of expression or process, wherein for example mask or screen cloth or its combination are passed through in the energy emission of ray form, thereby collide the zone of the wall with outer perimeter restriction with the mode of limited space.For example; UV radiating space constraint can have by the mask or the screen cloth transparent or open base area (unscreened zone) of the encirclement of the zone (zone of conductively-closed) of UV are not realized thoroughly through use; Shown in Fig. 1-9 of US patent 6,627,124 (it is for reference that its full content is introduced this paper).Unscreened zone has by the wall that limits of perimeter outside of shielding area not.
" visibility tinting material " is meant lens staining (or painted) so that the user confirms the tinting material (material) of the position of contact lens easily in the inner clear solution of lens storage, sterilization or cleaning vessel.Known in this field can be with dyestuff and/or pigment as the visibility tinting material.
Terminology used here " fluid " expression material can be mobile as liquid.
Terminology used here " LbL coating " expression does not have covalently bound coating on contact lens or the half module, and they suffer through polyion (or charged) and/or the layer of uncharged material on lens or half module, and layer (" LbL ") formula deposition obtains.The LbL coating can be made up of one or more layers, preferably is made up of one or more layers bilayer.
" polyion material " used herein is meant the polymer materials with a plurality of charged groups or ionogen, for example polyelectrolyte, p-and the adulterated conductive polymers of n-type.The polyion material comprises polycation (having positive charge) and polyanion (having negative charge) material.
Term used herein " bilayer " uses in a broad sense; Comprise: a kind of coating structure that on contact lens or half module, forms, it is through alternately there not being particular order ground to apply one deck first polyion material (or charged materials) and apply one deck subsequently and have with the second polyion material (or charged materials) formation of the electric charge of the first polyion material opposite charge; Or a kind of coating structure that on contact lens or half module, forms, it is not form through alternately there being particular order ground to apply first kind of charged polyion material of one deck and the uncharged polymer materials of one deck or second kind of charged polymer materials.Should be noted in the discussion above that first kind of layer (above-mentioned) with the third coating can be intersected with each other in bilayer.
The formation of LbL coating can form through many modes on contact lens or half module, for example is described in US patent 6,451,871,6,719, in 929,6,793,973,6,811,805,6,896,926 (it is for reference that it is all introduced this paper).
The first layer of " innermost layer " used herein expression LbL coating, it is coated onto on the surface of contact lens or half module.
The last one deck or the individual layer of " end-blocking layer " used herein or " outermost layer " expression LbL coating, it is coated onto on contact lens or the half module.
" average contact angle " expression water contact angle (detecting through the Sessile sessile drop method), this is on average to obtain through the detected value with at least 3 independent contact lenses.
Here the term " surface hydrophilicity of raising " that uses about the contact lens that applies or " wetting ability of raising " are illustrated in the contact lens that the temperature higher than room temperature (about 22 ℃) apply and have littler average (water) contact angle of contact lens that applies than in room temperature; Wherein all contact lenses are to be processed by identical core material, and all coating solutions have identical composition.
Here after being illustrated in usefulness
(CIBA Vision) or Equivalent finger friction lens about the term " through the finger frictional experiment " that uses in the LbL coating on the contact lens, the dyeing area of lens is not compared with the dyeing area of the identical lens when not rubbing significantly to be increased.The dyeing experiment is the Sudan's black-dyeing experiment of in embodiment 1, describing.Preferably; After being illustrated in usefulness
(CIBA Vision) or Equivalent finger friction lens about " through the finger frictional experiment " that uses in the LbL coating on the contact lens; Average contact angle on the lens after the friction remains about 90 degree or littler; Preferred about 80 degree or littler; Further more preferably from about 70 the degree or littler, most preferably from about 60 the degree or littler.
Here about term " through repeating to press the heat experiment " the expression lens that use in the LbL coating on the contact lens about 121 ℃ press heat 5 times after; Each heat of pressing continues 30 minutes, and the dyeing area of lens significantly increases with not comparing at the dyeing area that does not repeat to press the identical lens when hot.The dyeing experiment is the Sudan's black-dyeing experiment of in embodiment 1, describing.Preferably; About " through repeating to press the heat experiment " used in the LbL coating on the contact lens be illustrated in lens about 121 ℃ press heat 5 times after; Each heat of pressing continues 30 minutes, and the average contact angle on the lens after the friction remains about 90 degree or littler, preferred about 80 degree or littler; Further more preferably from about 70 the degree or littler, most preferably from about 60 the degree or littler.
As used herein, " biocide " is meant the chemical of the for example term known in the art that can reduce or eliminate or suppress microorganism growth.The example of preferred biocide includes but not limited to antimicrobial metal (for example Ag, Au, Pt, Pd, Ir, Sn, Cu, Sb, Bi and Zn; Wherein Ag is most preferred); Contain antimicrobial metal nanoparticle (be size less than 1 micron, and contain at least a antimicrobial metal that exists with one or more oxidation state), the antimicrobial metal nanoparticle is (promptly; Basically process by antimicrobial metal and size less than 1 micron particle, for example Nano silver grain).
" the oxygen perviousness " of lens used herein is the speed that Oxygen Flow is crossed specific ophthalmic lens.Oxygen perviousness Dk/t uses the unit representation of Barrer/mm usually, and wherein t is the material mean thickness [mm of unit] on the whole survey area, and " Barrer/mm " is defined as:
[(cm
3Oxygen)/(cm
2) (second) (mm
2Hg)] * 10
-9
Lens material inherent " oxygen permeability " Dk does not rely on lens thickness.The inherent oxygen permeability is the speed that oxygen passes material.Oxygen permeability is unit representation with Barrer usually, and wherein " Barrer " is defined as:
[(cm
3Oxygen) (mm)/(cm
2) (second) (mm
2Hg)] * 10
-10
These are this area units commonly used.Therefore, for consistent with the use of this area, unit " Barrer " has the implication that is defined as above.For example, Dk is that 90Barrer (" oxygen permeability Barrer ") and thickness are that the Dk/t that the lens of 90 microns (0.090mm) have is 100Barrer/mm (oxygen perviousness Barrer/mm).According to the present invention, high oxygen permeability representes that with apparent oxygen permeability be 40Barrer or the more greatly material or the contact lens of characteristic at least, and this is that sample (film or lens) with 100 microns detects according to the coulometry described in the embodiment.
" ion permeability " that passes lens is relevant with Ionoton iontophoretic injection coefficient with the lonoflux spread coefficient.
Fick's law (Fick ' s law) is following to be confirmed the lonoflux diffusion coefficient D through using:
D＝-n’/(A×dc/dx)
N '=ion-transfer speed [mol/ minute] wherein
A=lens exposure area [mm
2]
D=lonoflux spread coefficient [mm
2/ minute]
Dc=concentration difference [mol/L]
Dx=lens thickness [mm]
Ionoton iontophoretic injection FACTOR P is then confirmed through following formula:
In(1-2C(t)/C(0))＝-2APt/Vd
Wherein: the Na ion concentration of C (t)=in giving the body pond
The initial Na ion concentration of C (0)=in the donor pond
The A=membrane area promptly is exposed to the lens area in pond
The volume (3.0ml) of chamber, V=pond
The average lens thickness of d=in exposed region
The P=PQ
The lonoflux diffusion coefficient D is preferably greater than about 1.5 * 10
-6Mm
2/ minute, yet more preferably greater than about 2.6 * 10
-6Mm
2/ minute, most preferably greater than about 6.4 * 10
-6Mm
2/ minute.
Known that the last motion of the eye that needs lens exchanges to guarantee good tears, and finally guaranteed good corneal health.Ion permeability is that eye is gone up one of indication parameter that moves, and this is because the ionic perviousness is considered to directly and the perviousness of water is proportional.
At US 6,451, find need not carry out the pre-treatment of complicated and time consumption in 871 to the core material surface for polyion property polymeric materials is combined make the medical device surface charging before with core material.Through simply with or the solution that makes medical device (for example contact lens) core material and first kind of polyion property polymeric materials contact with having with the solution of second kind of polyion property polymeric materials of first kind of polyion property polymeric materials opposite charges, can on medical device, form the surface property of multilayer LbL coating with the core material of improvement medical device.
Be surprised to find now, the temperature of coating solution with coating of hydrophobic backbone has remarkably influenced to wetting ability, integrity and the weather resistance that does not have covalently bound LbL coating to the contact lens.Along with the temperature of coating solution raises, the wetting ability of the gained coating on contact lens is strong (for example littler water contact angle), more complete (for example significantly still less or do not have sudan black dyeing), weather resistance better (can or repeat to press the heat experiment through the finger frictional experiment) more.Based on these beat all discoveries, developed a kind of improved LbL coating method, this method can with cost effectively and fast mode on contact lens, prepare the LbL coating of the wetting ability with raising, good integrity and excellent durability.
On the one hand; The present invention provides a kind of hydrophilic coating is coated to the method on the siloxanes aquogel contact lens; This method comprises: contact lens is contacted with first coating solution of temperature for about 45-95 ℃; Thereby form and the non-covalent undercoat that is connected of contact lens, wherein first coating solution comprises the polyion material with first hydrophobic backbone and a plurality of ionizable or charged side group, and wherein undercoat contains at least one strata ionic material; (b) said contact lens is contacted with second coating solution of temperature for about 45-95 ℃; Thereby on undercoat, form finishing coat; Wherein second coating solution contains the uncharged hydrophilic polymer with second hydrophobic backbone, and wherein finishing coat contains one deck hydrophilic polymer at least.
According to the present invention, can contact and the LbL coating is coated onto on the siloxanes aquogel contact lens with one or more coating solutions through make lens according to the whole bag of tricks, for example these methods are referring to USP 6,451; 871,6,719,929,6,793; 973,6,811,805,6; 896,926, it is for reference that they are all introduced this paper.
Contact lens can carry out through contact lens is immersed in the coating solution with contacting of coating solution, or through carrying out with coating solution spraying contact lens.A kind of coating processes comprises and only carries out dip-coating and randomly flood-rinse step.Another kind of coating processes comprises and only sprays and spray-rinse step.But those skilled in the art can use many other to comprise the various array modes of spraying and dip-coating and rinse step.
For example, on contact lens, form by the only dip-coating method of the double-deck LbL coating of forming of one deck at least and may further comprise the steps: (a) in first kind of coating solution with first kind of coating of contact lens immersion; (b) randomly through half module being immersed in the water and half module is carried out rinsing; (c) lens are immersed in second kind of coating solution of second kind of coating, thereby the first layer that forms first kind and second kind coating is double-deck; (d) randomly lens are carried out rinsing through lens are immersed in the washing lotion; (e) randomly repeating step (a) to (d) repeatedly to form extra bilayer.Thicker LbL coating can through preferably repeatedly repeating step (a) to (d) prepare.
The immersion time for each coating and optional rinse step can continue less than about 1 minute, and this is because application temperature is higher.Preferably, the immersion of core material in coating solution continues the about 3-20 time of second, more preferably from about 5-10 second.Rinsing can use a plurality of rinse step to accomplish, but if desired, single rinse step is enough.
Another is used on contact lens forming by the coating method of the double-deck LbL coating of forming of one deck at least and for example comprises a series of spraying technologies.For example, only spraying coating process generally comprises following steps: the surface that (a) sprays contact lens with first kind of coating solution of first kind of coating; (b) randomly through with rinsing solution spraying lens surface to carrying out rinsing in this surface; (c) spray the surface of contact lens with second kind of coating solution of second kind of coating, thereby the first layer that forms first kind and second kind coating is double-deck; (d) through with rinsing solution spraying lens surface to carrying out rinsing in this surface; (e) randomly repeating step (a) to (d) is repeatedly.
Spraying can be accomplished through being selected from following technology: air-assisted spray and distribution technology; UW assistant spray and distribution technology; Piezoelectricity assistant spray and distribution technology, electromechanical jet printing technology, piezo jet typography; Adopt the piezo jet typography of hydraulic pressure, and the thermojet typography; And the location of distribution head on ophthalmic lens and the computer system of distribution applying liquid that can control spraying equipment.These spraying methods are described in USP 6,811, in 805.
Fig. 1 has shown a kind of equipment of embodiment of the present invention.Siloxanes aquogel contact lens 4 is arranged in pond 6, and this pond has three fluid intakes (1,2,3) that are connected with spray equipment and outlet 5 that is positioned at 6 tops, pond.Under computer control, first kind of solution 1 (for example PAA solution) is introduced into earlier in the pond to apply one deck PAA, then, for example after 5 seconds, 6 takes out solution 1 via the outlet 5 that is positioned at the bottom from the pond.Then, with water via inlet 2 introducing ponds 6, thereby the said lens of rinsing 6 take out water from the pond then.At last, solution 3 (for example PVP solution) is introduced into pond 6 via inlet 3, thereby on lens, applies the PVP finishing coat, then the 6 taking-up solution 3 from the pond.Coating time and rinsing time can be by computer control.
Fig. 2 has shown the equipment of another kind of embodiment of the present invention.This design and the difference of equipment shown in Figure 1 be each apply with rinsing solution be 6 bottom introducing from the pond.The solution materials flow will be in pond 6 relay lens.Coating and rinse operation can fully automatically be carried out under the control of computingmachine.Coating time and rinsing time can be by computer control.
According to the present invention, the coating that is used to form the LbL coating need have hydrophobic backbone.Though the contriver does not hope to receive the restriction of any particular theory; But think through hydrophobic-hydrophobic interaction; Intensive can take place with the hydrophobic surface zone of siloxanes aquogel contact lens and interact in the hydrophobic main chain of coating, thereby coating is fixed on the lens surface.Think also that under higher application temperature the molecule of coating possibly be able to more closely contact with the hydrophobic surface zone of lens, when temperature reduces, " is hunted down " there then.
The temperature of coating solution preferably is higher than 50 ℃, more preferably is higher than 60 ℃, further more preferably is higher than about 70 ℃, most preferably is about 80 ℃ or higher.
Be used for polyion material of the present invention and comprise polyanionic polymer and polycationic polymer with hydrophobic main chain and charged or ionogenic side group.The polyion material is polyanionic polymer preferably.
Suitable polyanionic polymer is including, but not limited to ROHM (PAA), branched p 0 lypropylene acid, and polymethyl acrylic acid (PMA), ROHM or polymethyl acid copolymer, toxilic acid or fumaric acid multipolymer gather (styrene sulfonic acid) (PSS).The example of branched p 0 lypropylene acid comprises that the example from the multipolymer of
or
acrylic or methacrylic acid of Goodrich Corp. comprises the copolyreaction product of acrylic or methacrylic acid and vinyl monomer; Vinyl monomer comprises for example acrylic amide, N, N-DMAA or N-vinyl pyrrolidone.The polyanionic polymer that preferably has hydrophobic main chain is the ROHM or the PEMULEN TR2 of straight chain or branching.Preferred anionic polymer is the ROHM of straight chain or branching.In this respect, branched p 0 lypropylene acid is interpreted as the ROHM of expression through vinylformic acid polymerization acquisition in the presence of the divinyl compound of appropriate amount (minimum) or many vinyl compounds.
Example with polycationic polymer of hydrophobic main chain includes but not limited to: polyallylamine (PAH), and polymine (PEI), polyvinylamine gathers (vinyl benzyl-three-C
1-C
4Alkylammonium salt), polyvinylpyridine father-in-law salt gathers the season thing.Above-mentioned polymkeric substance comprise in each case free amine form, its suitable salt form and any season form, if do not specialize.
Any suitable uncharged hydrophilic polymer with hydrophobic main chain can be used for the present invention.They are Z 150PH (PVA) preferably, the more preferably homopolymer of vinyl lactam, and at least a vinyl lactam exists or does not have the multipolymer under one or more hydrophilic ethylene base monomers, or their mixture.
PVA is a widely used high degree of biocompatibility material in ophthalmic product, especially for the wetting drop of eyepiece comfortableness or artificial tears (HypoTears for example
TMDeng).Can use all types of PVA, for example have low, in or those of high polyvinyl acetate contents.The Z 150PH that is used for the present invention is known, can for example obtain from KSE (Kuraray Specialties Europe) with trade(brand)name
.
According to the present invention, vinyl lactam has the structure of formula (I):
Wherein R is the alkylidene group with 2-8 carbon atom; R
1Be hydrogen, alkyl, aryl, aralkyl or alkaryl; Preferred hydrogen or have the low alkyl group of maximum 7 carbon atoms; The low alkyl group that more preferably has maximum 4 carbon atoms; For example methyl, ethyl or propyl group have the aryl of maximum 10 carbon atoms, or have the aralkyl or the alkaryl of maximum 14 carbon atoms; R
2Be hydrogen or low alkyl group, more preferably have the low alkyl group of maximum 4 carbon atoms, for example methyl, ethyl or propyl group with maximum 7 carbon atoms.
Preferred uncharged hydrophilic polymer is from vinyl lactam deutero-multipolymer, and said vinyl lactam is formula (I) heterocyclic monomer that in heterocycle, contains 4-6 carbon atom, or their mixture.Preferred uncharged hydrophilic polymer is from vinyl lactam deutero-multipolymer, and said vinyl lactam is formula (I) heterocyclic monomer that in heterocycle, contains 4 carbon atoms, or their mixture.Further preferred uncharged hydrophilic polymer is from vinyl lactam deutero-multipolymer, and said vinyl lactam is formula (I) heterocyclic monomer that in heterocycle, contains 4 carbon atoms, and R
1And R
2Be hydrogen or low alkyl group independently of one another, or their mixture.Most preferred uncharged hydrophilic polymer is PVP K120 (PVP).
According to the present invention, coating solution can prepare in every way.Preferably, coating solution can form through coating is dissolved in the water.The concentration of coating in solution generally can change according to used concrete material, required coat-thickness and many other factorses.Be typically rarer aqueous solution of preparation coating.For example, coating concentration can be about 0.0001-0.25 weight %, about 0.005-0.10 weight %, or about 0.01-0.05 weight %.
In order to change the various characteristics of coating, thickness for example can change the molecular weight of coating.Particularly, along with the raising of molecular weight, coat-thickness generally increases.
According to the present invention, the LbL coating contains the first kind of polyion material and the uncharged hydrophilic polymer with hydrophobic main chain that one deck at least has hydrophobic main chain.First kind of polyion material be polyanionic polymer preferably.
In a more preferred embodiment, the LbL coating contains the innermost layer of at least one strata vinylformic acid (PAA) and the end-blocking layer of at least one layers of polyethylene base pyrrolidone.
In a preferred embodiment of the invention, the inventive method further be included in contact lens contact with first kind of coating solution before with a kind of organic solvent or ORGANIC SOLVENT MIXTURES step at room temperature rinsing contact lens.
In a further preferred embodiment, this method further be included in room temperature with water rinse by the step of the contact lens of first kind of polyion coated materials.
On the other hand; The present invention provides a kind of method of making the siloxanes aquogel contact lens; This method may further comprise the steps: (a) form material casting siloxanes aquogel contact lens from the siloxanes aquogel contact lens, wherein said siloxanes aquogel contact lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer has the siliceous big monomer of ethylenically unsaturated group; Crosslinkable siliceous prepolymer, and their mixture; (b) contact lens is contacted with first coating solution of temperature for about 45-95 ℃; Thereby form and the non-covalent undercoat that is connected of contact lens; Wherein first coating solution comprises the polyion polymer materials with first hydrophobic backbone and a plurality of ionizable or charged side group, and wherein undercoat contains at least one strata ionic material; (c) said contact lens is contacted with second coating solution of temperature for about 45-95 ℃; Thereby on undercoat, form finishing coat; Wherein second coating solution contains the uncharged hydrophilic polymer with second hydrophobic backbone, and wherein finishing coat contains the said hydrophilic polymer of one deck at least.
" silicone hydrogel lens formation material " is meant can be through the polymerisable compound of thermofixation or photochemical curing or the crosslinked silicon-containing polymer of chemosetting (being polymerization and/or crosslinked) acquisition.Lens-forming material is well known to a person skilled in the art.According to the present invention, silicone hydrogel lens forms material and contains at least a siliceous monomer or big monomer, maybe can be any lens formulation that is used to make soft-contact lens.Exemplary lens formulation includes but not limited to following batching: Lotrafilcon A, Lotrafilcon B, Etafilcon A, Genfilcon A, Lenefilcon A, Polymacon, Acquafilcon A, Balaflcon, Senofilcon A etc.Lens-forming material can also comprise other component, for example initiator (for example light trigger or thermal initiator), visibility tinting material, UV-blocker, photosensitizers etc.Preferably, be used for silicone hydrogel lens formation material of the present invention and comprise siliceous big monomer.
The example of silicon-containing monomer includes but not limited to: the methacryloxy alkylsiloxane; 3-methacryloxypropyl pentamethyl disiloxane; Two (methacryloxypropyl) tetramethyl--sily oxide; The YSR 3286 of monomethyl acrylization; The end capped YSR 3286 of sulfydryl; N-[three (trimethylsiloxy group) silyl propyl group] acrylic amide; N-[three (trimethylsiloxy group) silyl propyl group] USAF RH-1; Three (pentamethyl-two siloxies)-methacrylate based propyl silanes of 3-(T2) and methylacrylic acid three (trimethylsiloxy) silyl propyl diester.The monomer that preferably contains siloxanes is called TRIS, and this is 3-methacryloxypropyl three (trimethylsiloxy group) silane, and is represented by CAS No.17096-07-0.Said term " TRIS " also comprises the dimer of 3-methacryloxypropyl three (trimethylsiloxy group) silane.
Any suitable big monomer that contains siloxanes with ethylenically unsaturated group can be used to prepare the siloxanes aquogel material.The big monomer that especially preferably contains siloxanes is selected from US 5,760, the big monomer A described in 100, big monomers B, big monomer C and big monomer D, and it is for reference all to introduce this paper here.The big monomer that contains two or more polymerizable groups (vinyl groups) also can be used as linking agent.Also can use diblock and the big monomer of three blocks formed by YSR 3286 and polyoxyalkylene.These big monomers can be by propenoate, methacrylic ester or vinyl monofunctional or Bifunctionalized.T 46155/polydimethylsiloxane//polyoxyethylene the segmented copolymer that for example, can use methacrylate-terminated is to improve oxygen permeability.
The example of siliceous prepolymer includes but not limited to disclose those that describe in US 2001-0037001A1 and the USP 6,039,913 at USP, and it is for reference that its full content is introduced this paper.Preferably, the prepolymer that uses is in the present invention purified according to known mode own in advance, for example through with organic solvent (for example acetone) deposition, filters and washing, in suitable solvent, extracts dialysis or ultrafiltration, wherein especially preferably ultrafiltration.Through these purifying techniques, prepolymer can obtain with extremely pure form, for example obtains with spissated aqueous solution form, and it does not contain or do not contain at least basically reaction product (for example salt) and raw material (for example unpolymerized component).As the method for the purification prepolymer that preferably uses in the methods of the invention, ultrafiltration can be carried out according to known mode itself.Ultrafiltration can repeatedly be carried out for example 2-10 time.Perhaps, ultrafiltration can be carried out up to reaching selected purity continuously.The purity principle of selecting is high as much as possible.The suitable method that detects purity is the concentration of the dissolved salt that for example obtains as by product, and this can measure according to known way simply.
According to the present invention, siloxanes aquogel forms material can also comprise hydrophilic ethylene base monomer.In fluid composition of the present invention, can use the almost any hydrophilic ethylene base monomer that can be used as softening agent.Wherein preferred hydrophilic monomer is N; N-DMAA (DMA), methylacrylic acid 2-hydroxyethyl ester (HEMA), hydroxyethyl acrylate, vinylformic acid hydroxypropyl ester, hydroxypropyl methacrylate (HPMA), methylacrylic acid 2-hydroxy-propyl ester trimethylammonium hydrochlorinate ammonium, dimethylaminoethyl methacrylate (DMAEMA), dimethyl aminoethyl-USAF RH-1, acrylic amide, USAF RH-1, vinyl carbinol, vinyl pyridine, glyceral methacrylate, N-(1; 1-dimethyl--3-oxygen-butyl) acrylic amide, N-vinyl-2-Pyrrolidone (NVP), vinylformic acid, methylacrylic acid and N, N-DMAA (DMA).
Siloxanes aquogel forms material also can comprise hydrophobic monomer.Through in polymerisable fluid composition, introducing a certain amount of hydrophobic vinyl monomers, can improve the mechanical property (like Young's modulus) of resulting polymers.
Siloxanes aquogel forms material also can comprise biocide, preferred antimicrobial nanoparticle, more preferably Nano silver grain.
Siloxanes aquogel forms material also can comprise the wetting agent that can leach." wetting agent that can leach " expression does not have covalently bound wet material to the polymeric matrix of siloxanes aquogel contact lens.
Anyly can not can be used as the wetting agent that can leach in the present invention by cross-linked hydrophilic property polymkeric substance.Exemplary can not include but not limited to by cross-linked hydrophilic property polymkeric substance: Z 150PH (PVA), T 46155, polyoxyethylene/polyoxypropylene block copolymers; Polymeric amide; Polyimide, polylactone, the homopolymer of above-mentioned formula (I) vinyl lactam; The multipolymer of at least a above-mentioned formula (I) vinyl lactam when existing or not having one or more hydrophilic ethylene base monomers; The homopolymer of acrylic amide or USAF RH-1, the multipolymer that acrylic amide or USAF RH-1 and one or more hydrophilic ethylene base monomers form, or their mixture.
According to the present invention, silicone hydrogel lens forms material can further contain various components, for example linking agent.Chain-transfer agent, initiator, UV absorption agent, stopper, filler, vision staining agent (for example dyestuff, pigment or their mixture) etc., these are well known to those skilled in the art.
According to the present invention, it can be solution that silicone hydrogel lens forms material, or not solvent-laden liquid, or is melt in the temperature that is lower than 60 ℃.One skilled in the art will know that how preparing silicone hydrogel lens forms material.
The lens die that is used to make contact lens is well known to a person skilled in the art, for example is used for casting or rotational casting.For example, mould (being used for casting) generally comprises at least two mould sections (or part) or half module, i.e. first half module and second half module.First half module defines first moulding (or optics) surface, and second half module defines second moulding (or optics) surface.First and second half modules are designed to admit each other, make between first molded surface and second molded surface, to form the lens die cavity.The molded surface of half module is the mold cavity surface of mould, and directly contacts with lens-forming material.
As if the method that manufacturing is used for the mould part of casting contact lens generally well known to a person skilled in the art.The inventive method is not limited to the ad hoc approach of any formation mould.In fact, the method for any formation mould can be used for the present invention.First and second half modules can form for example injection moulding or foaming through various technology.The appropriate method that is used to form half module for example is described in USP 4,444,711 (Schad), 4,460,534 (Boehm etc.), 5,843,346 (Morrill) and 5,894,002 (Boneberger etc.), and it is for reference also they all to be introduced this paper.
The basic all material that is used to prepare mould known in this field can be used to produce the mould that is used to make contact lens.For example; Can use polymer materials for example Vilaterm, Vestolen PP 7052, PS, PMMA,
COC rank 8007-S10 (transparent amorphous multipolymer of ethene and norbornylene; From Ticona GmbH of Frankfurt; Germany and Summit, New Jersey) etc.Can use other material that can allow the UV light transmission, for example silica glass and sapphire.
In preferred embodiments, use the mould of reusable edible, and silicone hydrogel lens formation material solidifies formation siloxanes aquogel contact lens with photochemical mode under the space constraint of actinic radiation.The example of the mould of preferred reusable edible is a U.S. Patent application 08/274; 942 (on July 14th, 1994 submitted), 10/732; 566 (on October 10th, 2003 submitted), 10/721,913 (on November 25th, 2003 submitted) and USP 6,627; Those that describe in 124, it is for reference that they are all introduced this paper.
In a further preferred embodiment; Wherein lens-forming material is solution (being dissolved in the mixture or organic solvent of water, water and water miscibility organic solvent); Not solvent-laden liquid, or choose the melt that in the presence of other component, has one or more siliceous prepolymers of ethylenically unsaturated group wantonly; Use the mould of reusable edible, and lens-forming material solidifies with photochemical mode under the space constraint of actinic radiation, thereby form painted contact lens.Those that the example of siliceous prepolymer includes but not limited in US 2001-0037001A1 and the USP 6,039,913 to describe, it is for reference that they are all introduced this paper.The example of the mould of preferred reusable edible is at U.S. Patent application 08/274; 942 (on July 14th, 1994 submitted), 10/732; 566 (on October 10th, 2003 submitted), 10/721,913 (on November 25th, 2003 submitted) and USP 6,627; Those that describe in 124, it is for reference that they are all introduced this paper.
In this case, lens-forming material is put into the mould of being made up of two half modules, two half module not contacts each other, but have the thin gap of annular between them.This gap is connected with die cavity, thereby excessive lens material can flow in the gap.Replacement can only expendable polypropylene molds; Can use quartz, glass, the sapphire mould of reusable edible; This is because after producing lens; These moulds can make water or suitable solvent remove uncrosslinked prepolymer and other resistates fast and effectively, and can use dry air.The mould of reusable edible also can be processed (the transparent amorphous multipolymer of ethene and norbornylene by
COC rank 8007-S10; From Ticona GmbH of Frankfurt; Germany and Summit, New Jersey).Because the reusable edible property of half module can be expanded higher design in their production period, thus the mould of acquisition very high degree of precision and reproducibility.Because half module not contact each other in the zone that will produce lens (being die cavity or actual die surface) is so got rid of the infringement that is caused by contact.This has guaranteed the high work-ing life of mould, the high circulation ratio of the contact lens that this has also guaranteed to produce especially.
Two opposed surface of contact lens (front surface with back surface) are limited two die surfaces, and the edge is the space constraint qualification through actinic radiation, is not to be limited mold wall.Generally; Only the lens-forming material within the projection institute localized area of the wall that is limited by the peripheral boundary of two die surfaces and space constraint is crosslinked; And on any peripheral boundary that is in space constraint with outside lens-forming material be not crosslinked; Thereby the edge of contact lens should be slick, accurately duplicates the size and the geometrical shape of the space constraint of actinic radiation.These methods of making contact lens are described in for example U.S. Patent application 08/274; 942 (on July 14th, 1994 submitted), 10/732; 566 (on October 10th, 2003 submitted), 10/721,913 (on November 25th, 2003 submitted) and USP 6,627; In 124, it is for reference that they are all introduced this paper.
The space constraint of actinic radiation (or space constraint of energy impact) can be carried out through covering the sort of mould that at least partly can not see through the energy of used particular form; Like U.S. Patent application 08/274; 942 (on July 14th, 1994 submitted) and USPs 6; 627,124 (it is for reference that they are all introduced this paper) are said; Or through the sort of mould that causes crosslinked form of energy and have high osmosis and have the mould part of the poor permeability of this energy being carried out at least one side; Like U.S. Patent application 10/732; 566 (on October 10th, 2003 submitted), 10/721; 913 (on November 25th, 2003 submitted) and USP 6,627,124 (it is for reference that they are all introduced this paper) are said.Being used for crosslinked energy is radiating capacity, particularly UV radiation, gamma-radiation, electron radiation or thermal radiation, and quantity of radiant energy is the form of substantially parallel bundle preferably, thereby reaches good restriction on the one hand, can effectively utilize energy on the other hand.
Can use in this respect of the present invention about the above-mentioned various embodiments of paint-on technique, coating and application temperature and preferred embodiment.
In yet another aspect, the present invention provides a kind of siloxanes aquogel contact lens of making according to the invention described above method.Contact lens of the present invention comprises sandwich layer siloxanes aquogel material and hydrophilic coating; Its center core layer siloxanes aquogel material is the copolymerization product that the siloxanes aquogel contact lens forms material; Wherein said siloxanes aquogel contact lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer; Siliceous big monomer with ethylenically unsaturated group, crosslinkable siliceous prepolymer, and their mixture; Wherein hydrophilic coating does not have covalently bound to sandwich layer siloxanes aquogel material; And comprise innermost layer and the outermost layer that one deck has the uncharged hydrophilic polymer of second hydrophobic backbone that one deck has the polyion polymer materials of first hydrophobic backbone; Wherein the siloxanes aquogel contact lens has the oxygen permeability of 40Barrer at least; With average water contact angle be 80 degree or littler be the wettable surface of characteristic and with can through the finger frictional experiment or to repeat to press heat experiment be the good coat weather resistance of characteristic.
Can use in this respect of the present invention about the above-mentioned various embodiments of paint-on technique, coating and application temperature and preferred embodiment.
In preferred embodiments; The siloxanes aquogel contact lens contains at least a biocide, preferred Nano silver grain; Present in an amount at least sufficient to have by reduce at least 5 times (>=80% inhibiting rates), preferably reduce at least 1-log (>=90% inhibiting rate), more preferably reduce at least the living microbial body of 2-log (>=99% inhibiting rate) (Pseudomonas aeruginosa (Pseudomonas aeruginosa) GSU#3 for example; Or streptococcus aureus (Staphylococcus aureus) ATCC#6538) antimicrobial acivity that characterizes preferably has long-term antimicrobial acivity (promptly directly contacting effectively antimicrobial acivity of long-time back with body fluid).The program determination that antimicrobial acivity is described in can the embodiment according to U.S. Patent application 10/891,407 (on July 14th, 2004 submitted), it is for reference that they are all introduced this paper.
" the long-term antimicrobial acivity " that here uses be illustrated at least 5 times, preferably at least 10 times, more preferably at least 20 times, more more preferably have at least 30 successive soaking/rinse cycle at least 5 times of reductions (>=80% inhibiting rate), preferably reduce at least 1-log (>=90% inhibiting rate), more preferably reduce at least the living microbial body of 2-log (>=99% inhibiting rate) (Pseudomonas aeruginosa GSU#3 for example; Or Staphylococcus aureus ATCC#6538); Wherein each circulation is included in middle about 24-72 of lens of immersion/rinsing hour time of phosphate buffered saline (PBS) (PBS); Like U.S. Patent application 10/891,407 (on July 14th, 2004 submitted) said (it is for reference that they are all introduced this paper).
Siloxanes aquogel contact lens of the present invention has wettable surface, and this is about 80 degree or littler, preferred about 70 degree or littler, more preferably from about 60 degree or littler, 50 degree or littler signs more preferably from about again by average water contact angle.
Siloxanes aquogel contact lens of the present invention have 40barrer at least, preferably at least about 50barrer, more preferably at least about 65barrer, more more preferably at least about the oxygen permeability of 80barrer.According to the present invention, oxygen permeability is the apparent oxygen permeability that detects according to the said program of embodiment (directly detecting when thickness is about 100 microns sample when detecting).
Siloxanes aquogel contact lens of the present invention can further have about 1.5MPa or littler Young's modulus, preferably about 1.2MPa or littler, 1.0MPa or littler more preferably from about, 0.4-1.0MPa more preferably from about again.
The lonoflux diffusion coefficient D of siloxanes aquogel contact lens of the present invention is preferably at least about 1.5 * 10
-6Mm
2/ minute, more preferably at least about 2.6 * 10
-6Mm
2/ minute, more more preferably at least about 6.4 * 10
-6Mm
2/ minute.
When complete hydration, the preferably about 18-55 weight of the water-content of siloxanes aquogel contact lens of the present invention %, more preferably from about 20-38 weight %.The water-content of siloxanes aquogel contact lens can be according to US 5,849, and the ontology of 811 descriptions detects.
Siloxanes aquogel contact lens of the present invention further contains the wetting agent that can leach.
Above-mentioned disclosure can make those skilled in the art's embodiment of the present invention.In order to make reader understanding's specific embodiments of the present invention and advantage better, below with reference to following examples explanation the present invention.
Embodiment 1
Surface hydrophilicity (wettability) experiment
Water contact angle on contact lens is that the routine of the surface hydrophilicity (or wettability) of contact lens is measured.Particularly, low water contact angle is corresponding to the stronger surface of wetting ability.The water contact angle of contact lens (Sessil drop) is to use VCA 2500XE contact angle detection device (from AST Inc., to be positioned at Boston, Massachusetts) to detect.This device can detect preceding or recall contact angle or sessile (static state) contact angle.Detection is on the contact lens of hydration fully, to carry out, and after drying up, carries out immediately.
The experiment of coating integrity
The integrity of the coating on surface in contact can detect according to following sudan black dyeing experiment.The contact lens of coating (LbL coating, plasma-coated, or any other coating) is immersed in the sudan black dye solution (sudan black vitamin E oil).The sudan black dyestuff is hydrophobic, and has the strong trend that is absorbed by hydrophobic material, or is adsorbed to the hydrophobicity lens surface or is positioned at the strong trend (for example siloxanes aquogel contact lens) on the lip-deep hydrophobic point of partial coating of hydrophobicity lens.If the coating on the hydrophobicity lens is complete, then should not observe stain on lens or in the lens.All lens that carry out this experiment are complete hydrations.
The coating durability experiment
Lens are pointed friction 30 times with
multi-usage lens nursing solution, use the salt water rinse then.Lens through the finger friction carry out sudan black experiment (that is, above-mentioned coating integrity experiment), thereby whether the inspection coating is still complete.Detect water contact angle to measure the coating weather resistance.
Perhaps, lens are carried out autoclaving 5 times at 121 ℃, continue 30 minutes at every turn, carry out sudan black dyeing experiment then and/or detect water contact angle.
Embodiment 2
ROHM (PAA) solution: molecular weight is that the solution of about 90,000 ROHM (from PolyScience) is in water, to form 0.05MPAA solution through the said material dissolves with appropriate amount to obtain.Based on the repeating unit among the PAA, calculate PAA concentration.After the dissolving, regulating the pH of polyanion PAA solution through adding 1N hydrochloric acid, is about 2.0 up to pH.
PVP K120 (PVP) solution: molecular weight is that the solution of about 24,000 PVP K120 (PVP K-25 is from Fluka) is in water, to form 0.01M PVP solution through the said material dissolves with appropriate amount to obtain.Based on the repeating unit among the PVP, calculate PVP concentration.After the dissolving, regulating the pH of PVP solution through adding 1N hydrochloric acid, is about 2.0 up to pH.
The siloxanes aquogel contact lens: uncoated siloxanes aquogel contact lens be through disclose according to U.S. Patent application 2001/0037001 said in mould the crosslinked preparation of compositions that contains siliceous prepolymer and light trigger.Siliceous prepolymer discloses 2001/0037001 described program preparation according to U.S. Patent application, and purifies through ultrafiltration.
Apply: in room temperature, uncoated lens are immersed ethanolic soln reach about 30 seconds, wherein ethanolic soln contains 1 gallon ETHYLE ACETATE, 1 gallon MIBK, 1 gallon hydrocarbon solvent, by 100 gallons of alcohol meters, drains ethanol then.The contact lens that will pass through the ethanol rinsing immerses PAA solution (0.05M in the temperature that is set at room temperature (about 25 ℃), 40 ℃ (solution temperature is about 36 ℃), 60 ℃ (solution temperature is about 52 ℃) or 80 ℃ (solution temperature is about 69 ℃) is bathed; PH2.0) reach about 5 seconds; From PAA solution, take out apace then, and drain.To be put into deionized water by the lens that PAA applies then, thereby in the quick rinsing of room temperature (1-2 second).(0.01mol/L pH2) reaches about 5 seconds in the temperature that is set at room temperature (about 25 ℃), 40 ℃, 60 ℃ or 80 ℃ is bathed, to immerse PVP solution then through the lens of water rinse.Then lens are taken out from PVP solution apace, and drain, immerse in the salt solution (PBS) to wash out PVP solution in room temperature then.These lens are put into the bottle of being filled by salt solution (PBS), and carried out autoclaving 30 minutes at 121 ℃.
Be characterized in the coating on the silicone hydrogel lens
The surface hydrophilicity of contact lens is through characterizing according to embodiment 1 said detection water contact angle.The integrity of the coating on contact lens is through detecting according to embodiment 1 described sudan black dyeing experiment.The weather resistance of the coating on contact lens through according to embodiment 1 described finger frictional experiment, carry out autoclaving 5 times at 121 ℃ (continue 30 minutes) at every turn, carry out sudan black dyeing experiment subsequently and detect.
Water contact angle result on the contact lens that applies is listed in the table 1.Discovery is not rubbing and/or during five autoclaving, all lens have the water contact angle less than 50 degree.Water contact angle reduces along with the rising of application temperature, is illustrated in high application temperature and can obtains the stronger coating of wetting ability and can not change coating solution to form.Through the lens of those coatings of finger friction, contact angle increases, and the coating that is illustrated on the lens receives some damages.But the coating in that high temperature obtains for example in the coating of 60 ℃ and 80 ℃ acquisitions, keeps almost the seldom integrity of variation, shown in the slight rising of water contact angle.High application temperature can be improved the weather resistance of the coating on lens.This finds further to carry out the data acknowledgement that five times those lens of autoclaving round-robin obtain through using.
Table 1
*Room temperature
The lens that apply do not rub or 5 autoclaving situation under sudan black dyeing experiment be presented at the lens that room temperature obtains and have by the discrete areas of sudan black dyeing; Show some by the painted point of sudan black at the lens of 40 ℃ of coatings, do not show observable dyeing at the lens of 60 ℃ and 80 ℃ coatings.The lens that apply at comparatively high temps have complete top coat.
Sample is also used O2Optix as a comparison
TMLens (they have plasma-coated) rub-sudan black dyeing experiment, do not observe dyeing.
Under friction situation; The sudan black dyeing experiment of the lens that apply be presented at lens that room temperature applies have vast scale by the zone of sudan black dyeing; Lens 40 ℃ of coatings have some by the painted zone of sudan black, in the almost demonstration dyeing of lens of 60 ℃ and 80 ℃ coatings.The lens that apply at comparatively high temps have than the significantly better weather resistance of the lens that apply in room temperature.
Under the situation of carrying out 5 autoclaving; The sudan black dyeing experiment of the lens that apply be presented at lens that room temperature applies have vast scale by the zone of sudan black dyeing; Lens 40 ℃ of coatings have some by the painted zone of sudan black, in the almost demonstration dyeing of lens of 60 ℃ and 80 ℃ coatings.The lens that apply at comparatively high temps have than the significantly better weather resistance of the lens that apply in room temperature.
Find can on the siloxanes aquogel contact lens, to form coating when high temperature, preferably about 60-80 ℃ when applying, its floating coat has good wettability (wetting ability), integrity and weather resistance.
Embodiment 3
Do not carry out any surface-treated O2Optix
TMLens apply at all temps with PAA and PVP.O2Optix
TMLens are processed by lotrafilcon B lens material.PAA and PVP solution are according to embodiment 2 said preparations.Coating processes is according to embodiment 2 said carrying out, and different is these lens to be immersed in PAA or the PVP solution reach 5 minutes.
The surface hydrophilicity of contact lens is through characterizing according to embodiment 1 said detection water contact angle.The integrity of the coating on contact lens is through detecting according to embodiment 1 described sudan black dyeing experiment.The weather resistance of the coating on contact lens through according to embodiment 1 described finger frictional experiment, carry out autoclaving 5 times at 121 ℃ (continue 30 minutes) at every turn, carry out sudan black dyeing experiment subsequently and detect.
Water contact angle result on the contact lens that applies is listed in the table 2.Discovery is not rubbing and/or during five circulation autoclaving, all lens have the water contact angle less than 60 degree.Water contact angle reduces along with the rising of application temperature, is illustrated in higher application temperature and can obtains the stronger coating of wetting ability and can not change coating solution to form.Through the lens of those coatings of finger friction, contact angle increases, and the coating that is illustrated on the lens receives some damages.But in the coating that high temperature obtains, for example the coating 60 ℃ and 80 ℃ acquisitions has less contact angle variation, and has the contact angle less than 90 degree, remains hydrophilic.By contrast, the coating that obtains in room temperature has the contact angle of about 116 degree, and after the finger friction, becomes hydrophobic.Higher application temperature can be improved the weather resistance of the coating on lens.This finds further to carry out the data acknowledgement that five times those lens of autoclaving round-robin obtain through using.After autoclaving 5 times, the coating that obtains in room temperature has the contact angle of about 75 degree, and contact angle has improved about 20 degree; And the coating that obtains at comparatively high temps has almost constant contact angle.
Table 2
*Room temperature
The lens that apply do not rub or 5 autoclaving situation under sudan black dyeing experiment be presented at the lens that room temperature obtains and have by the island-shaped area territory of sudan black dyeing, have some by the point of sudan black dyeing or do not show observable dyeing at the lens of 40 ℃, 60 ℃ and 80 ℃ coatings.The lens that apply at comparatively high temps have more complete top coat.
Under friction situation; The sudan black dyeing experiment of the lens that apply be presented at lens that room temperature applies have vast scale by the zone of sudan black dyeing; Lens 40 ℃ of coatings have some by the painted zone of sudan black, have some sudan blacks dyeing at the lens of 60 ℃ and 80 ℃ coatings.The lens that apply at comparatively high temps have than the significantly better weather resistance of the lens that apply in room temperature.
Under the situation of carrying out 5 autoclaving; The sudan black dyeing experiment of the lens that apply be presented at room temperature or 40 ℃ of coatings that lens had was similar with the situation carry out 5 autoclaving at them before by the painted zone of sudan black, the lens of 60 ℃ and 80 ℃ coatings almost demonstration dye.The lens that apply at comparatively high temps have than the significantly better weather resistance of the lens that apply in room temperature.
Find can on the siloxanes aquogel contact lens, to form coating when high temperature, preferably about 60-80 ℃ when applying, this coating has good wettability (wetting ability), integrity and weather resistance.
Although use particular term, apparatus and method to describe a plurality of embodiment of the present invention, this description only is used for illustrative purposes.Used language only is a descriptive language and nonrestrictive.Be to be understood that those skilled in the art can make conversion and change, and do not depart from the spirit or scope of the present invention in the appended claims.In addition, all respects that are to be understood that different embodiments can be carried out all or part of exchange.Therefore, the description of the spirit of said claim and the scope preferred form that should be not limited to here to be comprised.
Claims (16)
1. one kind is coated to the method on the siloxanes aquogel contact lens with hydrophilic coating, and this method may further comprise the steps:
(a) before contact lens contacts with first coating solution with a kind of organic solvent or ORGANIC SOLVENT MIXTURES at room temperature rinsing contact lens;
(b) contact lens that makes said rinsing and temperature are that 50-95 ℃ first coating solution contacts; Thereby form and the non-covalent undercoat that is connected of contact lens; Wherein first coating solution comprises the polyion material with first hydrophobic backbone and a plurality of ionogenic side groups; Wherein first coating solution has enough low pH to prevent ionogenic group generation ionization basically, and wherein undercoat contains at least one strata ionic material;
(c) in room temperature with water rinse by the contact lens of said polyion coated materials; With
(d) the said contact lens that in step (c), uses water rinse to cross in room temperature is contacted with second coating solution of temperature as 50-95 ℃; Thereby on the undercoat of said contact lens, form finishing coat; Wherein second coating solution contains the uncharged hydrophilic polymer with second hydrophobic backbone, and wherein finishing coat contains the said hydrophilic polymer of one deck at least.
2. the process of claim 1 wherein that the polyion material is the polyanionic polymer material.
3. the process of claim 1 wherein that the polyion material is the polycationic polymer material.
4. the method for claim 2; Wherein the polyanionic polymer material is selected from: the straight chain ROHM; Branched p 0 lypropylene acid, polymethyl acrylic acid, the multipolymer that vinylformic acid and at least a hydrophilic ethylene base monomer form; The multipolymer that methylacrylic acid and at least a hydrophilic ethylene base monomer form, and their mixture.
5. the method for claim 4; Wherein uncharged hydrophilic polymer is selected from: Z 150PH; The homopolymer of vinyl lactam; The multipolymer that at least a vinyl lactam and at least a hydrophilic ethylene base monomer form, and their mixture, therein ethylene base lactan has the structure of formula (I):
Wherein R is the alkylidene group with 2-8 carbon atom; R
1Be hydrogen, methyl, ethyl or propyl group, have the aryl of maximum 10 carbon atoms, perhaps have the aralkyl or the alkaryl of maximum 14 carbon atoms; R
2Be hydrogen, methyl, ethyl or propyl group.
6. the method for claim 4, wherein uncharged hydrophilic polymer is a PVP K120.
7. the method for claim 4; Wherein contact lens carries out the casting acquisition through silicone hydrogel lens being formed material; Wherein said silicone hydrogel lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer; Siliceous big monomer with ethylenically unsaturated group, crosslinkable siliceous prepolymer, and their mixture.
8. the method for claim 7; It is that one or more have the solution of the siliceous prepolymer of ethylenically unsaturated group, not solvent-laden liquid or melt that wherein said silicone hydrogel lens forms material; Randomly there is other component; Wherein lens-forming material carries out photochemical curing in the mould at reusable edible under the space constraint of actinic radiation, forms contact lens.
9. the method for claim 4, wherein the temperature of first and second coating solutions is 60-80 ℃.
10. the method for claim 4, wherein the temperature of first and second coating solutions is 70-95 ℃.
11. contact lens that obtains according to each method among the claim 1-10; Wherein said contact lens comprises sandwich layer siloxanes aquogel material; This sandwich layer siloxanes aquogel material is the copolymerization product that the siloxanes aquogel contact lens forms material; Wherein said siloxanes aquogel contact lens forms material and contains at least a following material that is selected from: siliceous vinyl monomer; Siliceous big monomer with ethylenically unsaturated group, crosslinkable siliceous prepolymer, and their mixture;
Wherein said contact lens has the oxygen permeability of 40Barrer at least,
Wherein hydrophilic coating has 80 degree or littler average water contact angles, and with can through the finger frictional experiment or to repeat to press heat experiment be the excellent durability of characteristic.
12. the contact lens of claim 11 wherein further comprises at least a biocide, presents in an amount at least sufficient to have by reducing at least 5 times, promptly >=80% the antimicrobial acivity of inhibiting rate sign.
13. the contact lens of claim 12, wherein biocide is a Nano silver grain.
14. the contact lens of claim 11, wherein contact lens has 1.5MPa or littler Young's modulus.
15. the contact lens of claim 11, wherein contact lens has 1.5x10 at least
-6Mm
2/ minute the Ionoflux diffusion coefficient D.
16. the contact lens of claim 11 wherein further comprises the wetting agent that can leach.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78758006P | 2006-03-30 | 2006-03-30 | |
| US60/787,580 | 2006-03-30 | ||
| PCT/US2007/065329 WO2007115027A2 (en) | 2006-03-30 | 2007-03-28 | Method for applying a coating onto a silicone hydrogel lens |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101410441A CN101410441A (en) | 2009-04-15 |
| CN101410441B true CN101410441B (en) | 2012-06-13 |
Family
ID=36954856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800111197A Expired - Fee Related CN101410441B (en) | 2006-03-30 | 2007-03-28 | Method for applying a coating onto a silicone hydrogel lens |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8044112B2 (en) |
| EP (1) | EP1999197B1 (en) |
| CN (1) | CN101410441B (en) |
| MY (1) | MY147491A (en) |
| SG (1) | SG170788A1 (en) |
| WO (1) | WO2007115027A2 (en) |
Families Citing this family (51)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5154231B2 (en) | 2005-02-14 | 2013-02-27 | ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド | Comfortable ophthalmic device and its manufacturing method |
| US9052529B2 (en) | 2006-02-10 | 2015-06-09 | Johnson & Johnson Vision Care, Inc. | Comfortable ophthalmic device and methods of its production |
| RU2464168C2 (en) * | 2007-04-06 | 2012-10-20 | Джонсон Энд Джонсон Вижн Кэа, Инк. | Methods of degassing monomer mixes in production of eye lens |
| US8119753B2 (en) | 2007-10-23 | 2012-02-21 | Bausch & Lomb Incorporated | Silicone hydrogels with amino surface groups |
| US20090171049A1 (en) * | 2007-12-27 | 2009-07-02 | Linhardt Jeffrey G | Segmented reactive block copolymers |
| TWI483996B (en) | 2009-12-08 | 2015-05-11 | Novartis Ag | A silicone hydrogel lens with a covalently attached coating |
| AU2011216361B2 (en) | 2010-02-16 | 2013-11-14 | Toray Industries, Inc. | Soft ocular lens having low moisture content and method for producing same |
| US9522980B2 (en) | 2010-05-06 | 2016-12-20 | Johnson & Johnson Vision Care, Inc. | Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same |
| SI2461767T1 (en) | 2010-07-30 | 2013-08-30 | Novartis Ag | Silicone hydrogel lenses with water-rich surfaces |
| US9170349B2 (en) | 2011-05-04 | 2015-10-27 | Johnson & Johnson Vision Care, Inc. | Medical devices having homogeneous charge density and methods for making same |
| SG11201400228WA (en) | 2011-10-12 | 2014-05-29 | Novartis Ag | Method for making uv-absorbing ophthalmic lenses by coating |
| US9505184B2 (en) | 2011-11-15 | 2016-11-29 | Novartis Ag | Silicone hydrogel lens with a crosslinked hydrophilic coating |
| JP2015502437A (en) | 2011-12-14 | 2015-01-22 | センプラス・バイオサイエンシーズ・コーポレイションＳｅｍｐｒｕｓ Ｂｉｏｓｃｉｅｎｃｅｓ Ｃｏｒｐ． | Silicone hydrogel contact lenses modified with lanthanides or transition metal oxidants |
| CA2859195C (en) | 2011-12-14 | 2016-09-27 | Semprus Biosciences Corp. | Imbibing process for contact lens surface modification |
| CA2859047C (en) | 2011-12-14 | 2017-03-21 | Semprus Biosciences Corp. | Redox processes for contact lens modification |
| CA2858730C (en) | 2011-12-14 | 2017-07-18 | Semprus Biosciences Corp. | Surface modified contact lenses |
| AU2012351991B2 (en) | 2011-12-14 | 2015-09-24 | Semprus Biosciences Corp. | Multistep UV process to create surface modified contact lenses |
| CA2874718A1 (en) | 2012-05-25 | 2013-11-28 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
| US9244196B2 (en) | 2012-05-25 | 2016-01-26 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
| US10073192B2 (en) | 2012-05-25 | 2018-09-11 | Johnson & Johnson Vision Care, Inc. | Polymers and nanogel materials and methods for making and using the same |
| EP2861413B1 (en) | 2012-06-14 | 2019-05-01 | Novartis AG | Azetidinium-containing copolymers and uses thereof |
| US9395468B2 (en) | 2012-08-27 | 2016-07-19 | Ocular Dynamics, Llc | Contact lens with a hydrophilic layer |
| SG11201504592YA (en) * | 2012-12-11 | 2015-07-30 | Novartis Ag | Method for applying a coating onto a silicone hydrogel lens |
| SG11201504763UA (en) | 2012-12-17 | 2015-07-30 | Novartis Ag | Method for making improved uv-absorbing ophthalmic lenses |
| US9950483B2 (en) | 2013-05-29 | 2018-04-24 | Novartis Ag | Method for determining the surface concentration of carboxyl groups on a lens |
| CN105917270A (en) | 2013-11-15 | 2016-08-31 | 视觉力学有限责任公司 | Contact lens with a hydrophilic layer |
| WO2015095157A1 (en) | 2013-12-17 | 2015-06-25 | Novartis Ag | A silicone hydrogel lens with a crosslinked hydrophilic coating |
| US11002884B2 (en) | 2014-08-26 | 2021-05-11 | Alcon Inc. | Method for applying stable coating on silicone hydrogel contact lenses |
| JP6483810B2 (en) | 2014-08-26 | 2019-03-13 | ノバルティス アーゲー | Poly (oxazoline-co-ethyleneimine) -epichlorohydrin copolymer and use thereof |
| AU2015360637B2 (en) | 2014-12-09 | 2019-08-22 | Tangible Science, Inc. | Medical device coating with a biocompatible layer |
| EP3268804B1 (en) | 2015-03-11 | 2020-11-04 | University of Florida Research Foundation, Inc. | Mesh size control of lubrication in gemini hydrogels |
| CN107850695B (en) * | 2015-07-20 | 2020-06-19 | Lg伊诺特有限公司 | Lens and lens assembly comprising the same |
| CA2992823C (en) | 2015-09-04 | 2019-10-29 | Novartis Ag | Method for producing contact lenses with durable lubricious coatings thereon |
| MX2018006690A (en) | 2015-12-03 | 2018-09-03 | Novartis Ag | Contact lens packaging solutions. |
| US10081142B2 (en) | 2015-12-15 | 2018-09-25 | Novartis Ag | Method for producing contact lenses with a lubricious surface |
| SG11201803726VA (en) | 2015-12-15 | 2018-06-28 | Novartis Ag | Method for applying stable coating on silicone hydrogel contact lenses |
| CN109690360B (en) | 2016-09-20 | 2023-04-25 | 爱尔康公司 | Method for producing contact lenses having durable lubricious coatings thereon |
| US10718960B2 (en) | 2016-10-31 | 2020-07-21 | Alcon Inc. | Method for producing contact lenses with wearing comfort |
| WO2018212063A1 (en) * | 2017-05-19 | 2018-11-22 | 東レ株式会社 | Contact lens composition, and contact lens and method for manufacturing same |
| TWI665263B (en) | 2017-06-07 | 2019-07-11 | 瑞士商諾華公司 | Silicone hydrogel contact lenses |
| AU2018279285B2 (en) | 2017-06-07 | 2020-12-17 | Alcon Inc. | Silicone hydrogel contact lenses |
| EP3447475B1 (en) | 2017-08-24 | 2020-06-17 | Alcon Inc. | Method and apparatus for determining a coefficient of friction at a test site on a surface of a contact lens |
| US11067831B2 (en) | 2017-10-30 | 2021-07-20 | Coopervision International Limited | Methods of manufacturing coated contact lenses |
| EP3724697B1 (en) | 2017-12-13 | 2022-01-12 | Alcon Inc. | Method for producing mps-compatible water gradient contact lenses |
| EP3647830B1 (en) * | 2018-10-30 | 2021-03-03 | UNICON Optical Co, LTD. | Hydrophilic coating method for contact lens surface |
| US11578176B2 (en) | 2019-06-24 | 2023-02-14 | Johnson & Johnson Vision Care, Inc. | Silicone hydrogel contact lenses having non-uniform morphology |
| US20210132411A1 (en) | 2019-11-04 | 2021-05-06 | Alcon Inc. | Contact lenses with surfaces having different softness |
| WO2021124099A1 (en) | 2019-12-16 | 2021-06-24 | Alcon Inc. | Wettable silicone hydrogel contact lenses |
| US20220032564A1 (en) | 2020-07-28 | 2022-02-03 | Alcon Inc. | Contact lenses with softer lens surfaces |
| WO2023069566A1 (en) * | 2021-10-20 | 2023-04-27 | Streck, Inc. | Method for spray coating a surface attached hydrogel |
| US20240092043A1 (en) | 2022-08-17 | 2024-03-21 | Alcon Inc. | Contact lens with a hydrogel coating thereon |
Family Cites Families (59)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168112A (en) | 1978-01-05 | 1979-09-18 | Polymer Technology Corporation | Contact lens with a hydrophilic, polyelectrolyte complex coating and method for forming same |
| ATE13642T1 (en) | 1980-01-10 | 1985-06-15 | Coopervision Inc | CROSSLINKED POLYMERS FOR CONTACT LENSES. |
| GB2102070A (en) | 1981-07-14 | 1983-01-26 | Anglo Netherland Engineering C | Assisted gas flow device |
| US4444711A (en) | 1981-12-21 | 1984-04-24 | Husky Injection Molding Systems Ltd. | Method of operating a two-shot injection-molding machine |
| US4570629A (en) | 1982-03-17 | 1986-02-18 | University Of Illinois Foundation | Hydrophilic biopolymeric copolyelectrolytes, and biodegradable wound dressing comprising same |
| US4460534A (en) | 1982-09-07 | 1984-07-17 | International Business Machines Corporation | Two-shot injection molding |
| JPH01158412A (en) | 1986-12-26 | 1989-06-21 | Daicel Chem Ind Ltd | Cleaning and preserving liquid for contact lens |
| US4941997A (en) | 1987-07-13 | 1990-07-17 | Ciba-Geigy Corporation | Amphiphilic azo dyes and molecular aggregates thereof |
| EP0329613A3 (en) | 1988-02-17 | 1991-06-05 | Ciba-Geigy Ag | Organic materials having non-linear optical properties |
| DE4026978A1 (en) | 1990-08-25 | 1992-02-27 | Bayer Ag | Coated substrates for electro=optical applications, etc. |
| JP3166298B2 (en) | 1991-10-04 | 2001-05-14 | 株式会社ダイヘン | Arc length control method for GMA welding |
| WO1995000618A1 (en) | 1993-06-18 | 1995-01-05 | Polymer Technology Corporation | Contact lens solution containing peo and cationic cellulose |
| US5518767A (en) | 1993-07-01 | 1996-05-21 | Massachusetts Institute Of Technology | Molecular self-assembly of electrically conductive polymers |
| US5894002A (en) | 1993-12-13 | 1999-04-13 | Ciba Vision Corporation | Process and apparatus for the manufacture of a contact lens |
| GB9415926D0 (en) | 1994-08-04 | 1994-09-28 | Biocompatibles Ltd | New materials |
| JPH07256844A (en) | 1994-03-18 | 1995-10-09 | Teijin Ltd | Laminated film and manufacture thereof |
| US5843346A (en) | 1994-06-30 | 1998-12-01 | Polymer Technology Corporation | Method of cast molding contact lenses |
| US5529787A (en) | 1994-07-07 | 1996-06-25 | Alza Corporation | Hydromorphone therapy |
| US5760100B1 (en) | 1994-09-06 | 2000-11-14 | Ciba Vision Corp | Extended wear ophthalmic lens |
| US5535908A (en) | 1994-11-04 | 1996-07-16 | Sheu; Miin-Tsang | Receptacle combination for milk powder |
| US5700559A (en) | 1994-12-16 | 1997-12-23 | Advanced Surface Technology | Durable hydrophilic surface coatings |
| WO1996037241A1 (en) | 1995-05-25 | 1996-11-28 | Minnesota Mining And Manufacturing Company | Process for producing biocompatible surfaces |
| US5700599A (en) * | 1996-01-12 | 1997-12-23 | Danko; Thomas | High absorption rate battery separator |
| US5882687A (en) | 1997-01-10 | 1999-03-16 | Allergan | Compositions and methods for storing contact lenses |
| US6011082A (en) | 1997-06-02 | 2000-01-04 | Pharmacia & Upjohn Ab | Process for the modification of elastomers with surface interpreting polymer networks and elastomers formed therefrom |
| GB9711818D0 (en) | 1997-06-06 | 1997-08-06 | Bausch & Lomb | Contact lens packing solutions and methods for improving the comfort of disposable contact lenses |
| TW429327B (en) | 1997-10-21 | 2001-04-11 | Novartis Ag | Single mould alignment |
| EP1046068B1 (en) | 1998-01-09 | 2003-05-21 | Novartis AG | Coating of polymers |
| US6451871B1 (en) | 1998-11-25 | 2002-09-17 | Novartis Ag | Methods of modifying surface characteristics |
| US6822016B2 (en) | 2001-09-10 | 2004-11-23 | Johnson & Johnson Vision Care, Inc. | Biomedical devices containing internal wetting agents |
| US7052131B2 (en) | 2001-09-10 | 2006-05-30 | J&J Vision Care, Inc. | Biomedical devices containing internal wetting agents |
| US6087415A (en) | 1998-06-11 | 2000-07-11 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with hydrophilic coatings |
| US6039913A (en) | 1998-08-27 | 2000-03-21 | Novartis Ag | Process for the manufacture of an ophthalmic molding |
| JP3105871B2 (en) | 1998-09-25 | 2000-11-06 | 埼玉日本電気株式会社 | Wireless device and wireless receiving method thereof |
| US20010036556A1 (en) | 1998-10-20 | 2001-11-01 | James S. Jen | Coatings for biomedical devices |
| US6719929B2 (en) | 2000-02-04 | 2004-04-13 | Novartis Ag | Method for modifying a surface |
| US6793973B2 (en) | 2000-02-04 | 2004-09-21 | Novartis Ag | Single-dip process for achieving a layer-by-layer-like coating |
| CA2401865C (en) | 2000-03-24 | 2010-01-12 | Novartis Ag | Crosslinkable or polymerizable prepolymers |
| US6689480B2 (en) | 2000-05-10 | 2004-02-10 | Toray Industries, Inc. | Surface-treated plastic article and method of surface treatment |
| BR0111395A (en) | 2000-05-30 | 2003-06-03 | Novartis Ag | Coated Items |
| US6589665B2 (en) | 2000-05-30 | 2003-07-08 | Novartis Ag | Coated articles |
| US6428839B1 (en) | 2000-06-02 | 2002-08-06 | Bausch & Lomb Incorporated | Surface treatment of medical device |
| CA2415871A1 (en) | 2000-08-24 | 2002-02-28 | Novartis Ag | Process for surface modifying substrates and modified substrates resulting therefrom |
| US6531432B2 (en) | 2000-12-07 | 2003-03-11 | Johnson & Johnson Vision Care, Inc. | Contact lens packaging solutions |
| JP2003066381A (en) * | 2001-05-23 | 2003-03-05 | Novartis Ag | System and method for processing object with liquid |
| US6811805B2 (en) | 2001-05-30 | 2004-11-02 | Novatis Ag | Method for applying a coating |
| US6827966B2 (en) | 2001-05-30 | 2004-12-07 | Novartis Ag | Diffusion-controllable coatings on medical device |
| US6815074B2 (en) | 2001-05-30 | 2004-11-09 | Novartis Ag | Polymeric materials for making contact lenses |
| US6858248B2 (en) | 2001-05-30 | 2005-02-22 | Novartis Ag | Method for applying a coating to a medical device |
| US7879267B2 (en) | 2001-08-02 | 2011-02-01 | J&J Vision Care, Inc. | Method for coating articles by mold transfer |
| US7402318B2 (en) | 2001-11-14 | 2008-07-22 | Novartis Ag | Medical devices having antimicrobial coatings thereon |
| AR038269A1 (en) | 2002-01-09 | 2005-01-12 | Novartis Ag | POLYMERIC ITEMS THAT HAVE A LUBRIC COATING, AND METHOD FOR MANUFACTURING THEM |
| WO2003066714A1 (en) | 2002-02-07 | 2003-08-14 | Lions Eye Institute Limited | Method for improving the surface quality of hydrogel articles |
| TW200304385A (en) | 2002-03-13 | 2003-10-01 | Novartis Ag | Materials containing multiple layers of vesicles |
| US6896926B2 (en) | 2002-09-11 | 2005-05-24 | Novartis Ag | Method for applying an LbL coating onto a medical device |
| US6926965B2 (en) | 2002-09-11 | 2005-08-09 | Novartis Ag | LbL-coated medical device and method for making the same |
| US8172395B2 (en) | 2002-12-03 | 2012-05-08 | Novartis Ag | Medical devices having antimicrobial coatings thereon |
| US8309117B2 (en) | 2002-12-19 | 2012-11-13 | Novartis, Ag | Method for making medical devices having antimicrobial coatings thereon |
| US6964580B1 (en) * | 2004-07-14 | 2005-11-15 | Datech Technology Co., Ltd. | Cable strain-relief member for a PC fan |
-
2007
- 2007-03-21 US US11/726,194 patent/US8044112B2/en not_active Expired - Fee Related
- 2007-03-28 SG SG201102197-9A patent/SG170788A1/en unknown
- 2007-03-28 WO PCT/US2007/065329 patent/WO2007115027A2/en active Application Filing
- 2007-03-28 CN CN2007800111197A patent/CN101410441B/en not_active Expired - Fee Related
- 2007-03-28 EP EP20070780747 patent/EP1999197B1/en not_active Not-in-force
-
2008
- 2008-09-19 MY MYPI20083686A patent/MY147491A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007115027A3 (en) | 2008-03-20 |
| US20070229758A1 (en) | 2007-10-04 |
| MY147491A (en) | 2012-12-14 |
| US8044112B2 (en) | 2011-10-25 |
| CN101410441A (en) | 2009-04-15 |
| SG170788A1 (en) | 2011-05-30 |
| EP1999197B1 (en) | 2014-08-13 |
| WO2007115027A2 (en) | 2007-10-11 |
| EP1999197A2 (en) | 2008-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101410441B (en) | Method for applying a coating onto a silicone hydrogel lens | |
| EP1046068B1 (en) | Coating of polymers | |
| US7566746B2 (en) | Biomedical devices having improved surface characteristics | |
| JP5064498B2 (en) | Method for producing a silicone hydrogel contact lens with good coating durability | |
| US8142835B2 (en) | Method for coating silicone hydrogels | |
| CN103038699B (en) | A silicone hydrogel lens with a crosslinked hydrophilic coating | |
| CN103917899B (en) | By being coated with the method for preparing UV absorbability eye-use lens | |
| JP5068765B2 (en) | Method for producing silicone hydrogel | |
| CN107532038A (en) | For producing the method in the haptic lens thereon with durable lubricant coating | |
| CN103597378A (en) | Silicone hydrogel lenses with nano-textured surfaces | |
| CN106715101B (en) | Method for applying stable coating in silicone hydrogel contact lens on piece | |
| WO2009115477A2 (en) | Coating process for ophthalmic lenses | |
| CN104871036A (en) | Method for making improved uv-absorbing ophthalmic lenses | |
| CN105829081A (en) | A silicone hydrogel lens with a crosslinked hydrophilic coating | |
| CN108710221A (en) | Ophthalmic lens and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: NOVARTIS CO., LTD. Free format text: FORMER NAME: NOVARTIS AG |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Basel, Switzerland Patentee after: NOVARTIS AG Address before: Basel, Switzerland Patentee before: Novartis AG |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191216 Address after: Fribourg Patentee after: ALCON, Inc. Address before: Basel, Switzerland Patentee before: NOVARTIS AG |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120613 |